The Parisian club has now secured the prestigious cup on 14 separate times.
Paris Saint-Germain needed a stoppage-time leveler followed by a successful spot-kick decider to overcome Marseille in the Gulf and capture a fourth straight French Super Cup title.
The European champions appeared to be sailing towards a comfortable triumph in the showdown between the French league winners and the Coupe de France holders after the French winger opened the scoring early on.
Yet, the southern French side struck two times in the closing moments to seize a shock lead. First, the English forward scored from the spot-kick, before the defender inadvertently directed the ball into his own net for an own goal.
In a remarkable twist of events, Goncalo Ramos grabbed a crucial equaliser in the dying seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, saving decisive kicks from O'Riley and Traore.
In the shootout, Ramos, the midfielder, the full-back, and Desire Doue all converted successfully for PSG to seal a convincing shootout victory.
The record champions PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now lifted this competition for the 12th time in the past 13 seasons.
